Prevention of corrosion in hydrogen fluoride catalytic organic reactions



Nov. 2, 1948 A. WACHTER 2,452,812

I Qi PREVENTION 0F CORROSION IN HYDROGEN FLUORIDE i I I CATALYTIC ORGANIC REACTIONS Original Filed Jan 14, 1944 Frad'io na'l'or Aarcin Wac' h+r Patented Nov. 2,1948

NITED STATES PATENT ore-lea PREVENTION OF CORROSION IN HYDRO- GEN FLUORIDE CATALYTIC ORGANIC RE- ACTIONS Aaron Wachter, Berkeley, Callt, assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware Original application January 14, 1944, Serial No.

518,273. Divided and this application December 26, 1946, Serial No. 718,585

16 Claims. (01.260-6834) This invention relates to the execution of organic chemical reactions with the aid of hydrogen fluoride and relates more particularly to improvements in the execution of catalytic hydrocarbon reactions in the presence of catalysts com prising hydrofluoric acid.

Hydrogen fluoride finds application as a reagent and/or catalyst in an ever-increasing number of organic chemical processes. In the field of hydrocarbon chemistry it is used as a catalyst in a wide variety of catalytic hydrocarbon conversions important in the synthesis of specific individual hydrocarbons as well as in the production of valu-,

able hydrocarbon motor fuels, lubricants, solvents, etc. Specific hydrocarbon conversion processes wherein hydrogen fluoride finds application as a catalyst comprise alkylation, polymerization, condensation, dehydrogenation, isomerization, etc.

Conditions-under which the hydrogen fluoride possibility or economic infeasibility of preventing the formation in, or the entry into the system of any traces of water in large scale operation. The presence of water in varying amounts, generally encountered in large scale operation, convide an improved process enabling the more emis used will vary considerably with the nature of the particular conversion process and the particular material treated therein. Thus, hydrogen fluoride is used as a catalyst both in the liquid phase as well as in the gaseous phase, andat temperatures ranging, for example, from about '40 C. to as high as about 350 C. Though often used per se, hydrogen fluoride may be employed in the presence of certain added materials such as, for example boron halides, functioning as a prometer, complement, or modifier of itscatalytic Though hydrogen fluoride in the completely anhydrous form is often referred to as having but little corrosive action upon many metal surfaces,'its effect under practical operating conditions, particularly on the more readily available and less costly materials of construction such as f the ferrous metal-containing materials, is gen erally suiflciently pronounced to influence decidedly the efflciency of the process. Such detrimental eflect is not l-imted to considerableshortenlng bf-the life of costly equipment but includes the loss of catalyst and the promotion, to an undue degree, of undesirable side reactions by the iron fluoride formed as a result of the corrosive action r of substantially reduced corrosive eifect upon. metal surfacesin contact therewith.

of the catalyst upon any ferrous metal-containing I surface in contact therewith. In practical operation the hydrogen fluoride is. however, often used in aqueous form, the water content of the acid varyirg from a trace to asmuch as 20% and more. Even in processes wherein the use of the catalyst in the anhydrous form is theoretically preferred, the presence of small amounts of water will generallybe encountered, due either to practical imcient execution of organic reactions with the aid of catalysts comprising hydrogen fluoride wherein the substantial corrosion of metal-containing surfaces incontact with said catalyst, inherent in processes used heretofore, is reduced to at least a substantial degree.

Another object of the present invention is the provision of an improved process for the more-eh ficient execution of catalytic hydrocarbon conversions with the aid of catalysts comprising hydrogen fluoride wherein the substantial corrosion of metal-containing surfaces in contact with said catalyst inherent in processes used heretofore is reduced to at least a substantial degree.

Another object of the invention is the provi sion of an improved process for the more efflcient alkylation of hydrocarbons with the aid of catalysts comprising hydrogen fluoride. A still further object of the invention is the provision of a hydrogen fluoride-containing catalyst In accordance with the present invention serious difllculties heretofore encountered in the execution of organic reactions with the-aid of catalysts comprising hydrogen fluoride are ob"- viated to at least a substantial degree, andimproved efliciency is attained by maintaining in the catalyst a metal of groups IV and V' of the periodic table. By the term metals as used throughout the specification and appended claims, it, is intended to include the eleme arsenic and antimony.

'The metals of groups IV and V are not nec'es sarily equivalent in the degree to which theadvantage of their-addition to the catalyst is-obtained. Some of the metals are more effective in their corrosion-inhibiting properties than others; their comparative effect in this regard 'being'to some exten determined by the severity of operating conditi ns and the composition of the metal surface in contact with the catalyst. Similarly, the amount of a 'sp eciflc inhibitor metal to be maintained within the catalyst will vary in accordance with variations in operating conditions and composition of the metal surfac in contact therewith. In general, when the metal surface in contact with the reactants comprises a ferrous metal surface, the concentration of the inhibitor metal to be maintained in the reaction zone will be from about 0.01% to about 20%, and preferably from about 0.1% to about by weight of the catalyst.

Of the metals of groups IV and V, antimony, arsenic and bismuth are preferred. The inhibitor metal need not necessarily be introduced into the catalyst or into the system in the uncombined or metallic form but may be employed in the form of a suitable compound thereof. Suitable compounds of the inhibitor metals comprise the metal in chemical combination with one or more of the halides such as the chlorides, bromides and fluorides,. for example, SbClaySbFa, SbBra, SbCh, SbCls. SbFs, SbBrs, BiClz, BiBrz, BiCla, BiFa, BiBra, B1014. BiF4, SnCls; halide salts of the inhibitor metals comprising more than one type of halide atom, for example, SbBrFl, antlmony fluorochlorides.

Although it is generally suflicient to effect the addition to the catalyst, or the introduction into the system, of but one of the inhibitors, more than one of these compounds may be added to obtain suppression of corrosion to a desired degree. The inhibitor-compound may also be employed in the form of an admixture or even a chemical combination with organic compounds. Thus, inhibitor metal-containing sludge recovered from a catalytic conversion in the presence of hydrogen fluoride wherein the metal was used as a corrosion inhibitor may be recycled to the inlet of the reaction zone; or the inhibitor metalcontaining sludge obtained from an entirely separate refinery operation wherein the metal was used as catalyst, treating agent or the like may suitably comprise the inhibitor metal-containing compound utilized in accordance with the present invention. For example, an antimony trichloridecontaining sludge obtained in the isomerization orallrylation of hydrocarbons, or in similar operations with the aid of metal halide-containing catalysts, may be utilized as a suitable antimonycontalning inhibitor compound in accordance with the present invention.

The inhibitor metal in combined form may be introduced directly into the hydrogen fluoride catalyst or maybe introduced into the reaction zone in any suitable manner. It may' be introduced in the form of solid pieces; a, powder; as a slurry or a suspension in a suitable liquid medium such as, for example, a suspension in a contact with the inhibitor prior to, or in intermittent stages of, operation will generally not render such surfaces immune to subsequent severe corrosion by the hydrogen fluoride in the absence of the inhibitor. Since the catalyst and hydrocarbons are generally passed in continuous stream through the system, the continuous presence of the inhibitor within the system throughout the operation will generally require the substantially continuous addition of the inhibitor.

Though the ability of the added compound to dissolve in the hydrocarbon 'or in the hydrogen fluoride catalyst is not essential to the attainment of the desired results, those capable of solution to some degree in either the hydrocarbon or in the hydrogen fluoride, or in both, are nevertheless somewhat preferred.

example, ASCls, SbCla, BiCla, AsFs and SbFa. Preference of a particular compound of a suitable inhibitor metal may be governed by the physi al state of the compound under operating conditions. Thus, in a process utilizing the hydrogen fluoride in the liquid phase it may at times be desirable to use a compound which is liquid at relatively low temperatures, such as, for example, SbF's, AsFa, BiF3-3HF. On the other hand, when utilizing hydrogen fluoride in the gaseous phase at relatively low temperatures, the use Of a compound of a metal in gaseous form at relativelylow temperatures, for example, ASF5, is at times desired. In processes utilizing hydrogen fluoride in the gaseous phase at elevated temperatures such as, for example, in the catalytic polymerization of hydrocarbons in the presence of a catalyst comprising hydrogen fluoride, the use of the inhibitor in the form of a compound capable of vaporizing or subliming at. and preferably below, the conditions of operations are generally preferred. The compound of the inhibitor metal may be introduced into the hydrocarbon charge and vaporized therewith before introduction into the reaction zone in the vapor phase-type of operations, or it may be'caused to vaporize in the reaction .zone, or it may be vaporized and separately introduced into the reaction zone.

I Another advan ageous method for the introduchydrocarbon, a hydrocarbon fraction or a part of the hydrogen fluoride catalyst; as a solution tion of the inhibitor into the reaction zone in vapor phase-type of operation comprises introducing into the upper part of the reaction zone a, suspension or solution of the inhibitor in a liquid medium, for example, a hydrocarbon which may or may not vaporize at the conditions of operation.

In order to set forth more fully the nature of the invention, without, however, intending to limit the scope of organic reactions executed with the aid of hydrogen fluoride-containing catalysts to which it may be applied, it will be described in detail in its application to the liquid phase alkylation of hydrocarbons with reference to the attached drawing wherein the single fi ure showsa more or less diagrammatical elevational view of one form of apparatus suitable for the execution of the invention.

Hydrocarbons comprising an alkylatable hydrocarbon, for example, an isoparaflin, such as isobutane, is forced by means of pump I through valved line 2 into a conversion zone. Means for the introduction or withdrawal of heat from the hydrocarbons flowing through line 2 comprising, for example, an indirect heat exchanger 3, are provided. The reaction zone may comprise any suitable type of reactor, chamber or zone of reoperation. subjection of'the metal surface to stricted cross-sectional area enablin efilcient Compounds of inhibitor metals advantageous in this respect comprise, for

' the desired temperature.

- means such as, for example, a closed coil 8 may contact of catalyst and reactants at the desired reaction conditions. The reaction zoneunay comprise an elongated coil 4 positioned in a suitable housing enabling the maintenanceof the desired temperature within the coil. The housing may comprise a furnace structure or the like enabling the external contact of the coil with gaseous or The housing liquid heating or cooling media. may comprise an-enlarged chamber 5 provided with. suitable means for the maintenance therein of gaseous or liquid cooling or heating media at Heating or cooling be positioned within chamber 5. Additional means not shown in the drawing are provided for the maintenance of the liquid media at the desired temperature. a

An alkylating agent, for example, an olefinic hydrocarbon such as butene,- or a mixture of oleiinic hydrocarbons such as a mixture of butenes, is forced by means of pump 8. through i valved line 9, into line 2. Since it is desired to maintain a relatively low concentration of the alkylat-lng agent with respect to the parafiin throughout the conversion zone, it is generally preferred to introduce the olefin into the reaction zone at a plurality of points along the length thereof. Valved lines I'll, II and i2 are therefore provided to enable the injection of butenc into coil t at a plurality of points along the length thereof.

Hydrogen fluoride drawn from an outside source is forced by means of pump i5 through valved line it into line 2.v Within coil 4 the reactants are maintained under alkylation conditions conducive to the interaction of the paraflin and olefin with the formation of a branchedchain saturated hydrocarbon, the number of carbon atoms of which is equal to the summation of the carbon atoms contained in both atoms of the interacting paraiiin and olefin. In the present illustrative description the isobutane and butene will interact with the formation of an alkylate ciently high is maintained within coil 4 to keep at least a substantial part of the reactants in the liquid phase. The hydrogen fluoride introduced into the system may be in substantially anhydrous form or may contain water in amounts ranging from a trace up'to about 20% and higher.

The proportion of hydrogen fluoride catalyst introduced into the reaction zonemayvary between, for example, about 2% to about 75%. and generally between about. 15% and about 40%, by volume of the hydrocarbon charge.

Reaction products comprising alkylate, unreacted hydrocarbons and catalyst are passed from coil 4, through transfer line l8, into a liquid phase separator l9. Within separator iii a supernatant mediate points along the length thereof.

fraction comprising unreacted hydrocarbons is separated from a liquid fraction comprising isooctane-containing alkylate. The liquid fraction is withdrawn from reactor 23 through valved line 24 as a final product.

The vapor fraction is removed from fractionator 23 through valved line 26. A part or all of the vapor fraction is recycled by means of pump 21 through valved line 28 to line ,2. If desired, a part or all of the stream flowing through line 28 may pass through valved line 29 and condenser 30 into an accumulator 3|. In pas-sing through condenser 30. the stream is cooled to a temperature sufliciently low to condense C4 hydrocarbons. From accumulator 3i liquid is withdrawn through valved line 32 and may be passed in part or in its entirety through line 33 into line 28.. Uncondensed vapors and gaseous materials are eliminated from separator 3| through valved A corrosion inhibitor, comprised within the group defined above, is continuously introduced into line 2 and preferably into coil 4 at inter- Although any suitable method of introduction may be resorted to,in a preferred method of executing the process of the invention, a part of the hydrocarbon feed or hydrogen fluoride catalyst is passed through a suitable container, for example, a drum 36 containing the inhibitor compound. From drum 86 the stream containing the inhibitor in solution and/or in suspension is passed through valved line 31 into line 2, and through valved line 38 and branched lines 39, 40 and M into coil 4 at intermediate points along the length thereof, as well as into transfer line l8.

pound soluble in hydrogen fluoride. hydrogen.

fluoride may be by-nassed from line It through valved line 44 into line 43 and may compr se the only liquidpassed through drum 36. Often it i will be referable to introduce into the system as inhibitor com oun s of Groups IV or V such as certain fluorid wh ch are either not readily available or are diflicult to handle. In roduction into the reaction zone of compounds leading to the formation of these materials within the reaction zone is often not practical for reasons which comprise mechanical diihculty of introducing the compound into the-reactor and the violence ofthe resulting reaction under conditions prevailing in the reaction zone. In accord-' ance with the present invention these difficulties liquid layer comprising alkylate and unreacted hydrocarbons is separated from a lower liquid layer comprising the hydrogen fluoride. The lower layer is recycled by means of pump 20,

a fractionator 23. Within iractionator 23 a. vapor are obviated by maintaining in drum 36 vamore readily available compound of the metal, the fluorine-containing compound of which is desired such as, for example; AsCla. SbzOa, etc., and'passing therethrough suflicient hydrocarbon emanating from line 2 through line 43, and containing only sufficient hydrogen fluoride emanating from line 44 to provide an eiiluent hydrocarbon stream from drum 36 through line 31 containing a suiiicient amount of the fluorine-containing compound -of the inhibitor metal as for example AsFa,

SbFa, etc., to maintainthe desired concentration 7 of the inhibitor metal in the reaction zone. when operating in this wise, the ratio of hydrogen fluoride to hydrocarbon in the stream entering drum 36 will generally be substantially below that of the ratio of hydrogen fluoride to hydrocarbon in coil 4. In this wise by the passage of a hydrocarbon stream containing but a low content of hydrogen fluoride through drum 36, desirable fluorine-containing compounds of the inhibitor metals may be efficiently and safely produced within the system. in the amount required.

In a modification of the invention the vapors eliminated from the upper part of fractlonator 23 through line 26, and optionally the gaseous fraction eliminated from accumulator 3i through line 36, which generally will contain relatively small proportions of hydrogen fluoride in admixture with greater proportions of unconverted hydrocarbons, may be recycled in part or in their entirety through drum 36 to provide a part or all of the medium required to bring the inhibitor from drum 36 to coil 4. To this purpose valved lines 45 and 46 are provided leading from lines 84 and 26, respectively, to the low pressure side of a compressor 41. From the high pressure side of compressor 41 thecbmpressed stream passes through valved line 48 containing suitable cooling means such as, for example, a cooler 49, into line 63.

Under the above described conditions of operation. substantial improvement in efliciency of operation with atleast a substantial. degree of reduction of corrosion difliculties heretofore encountered, and a considerable increase in yield of alkylate per pound of catalyst used will be obtained.

Although some of the inhibitor is often introduced with the hydrocarbon stream into fractionator 23, particularly when a compo nd soluble in the hydrocarbon reactants is used, corrosion difficulties will, nevertheless, often be encountered unless a ditional amounts of the inhibitor are introduced into fractionator 2 3. In accordance with the invention a part of the eflluent from drum 36 comprising the inhibitor, dissolved or suspended in a suitable liquid medium, is passed from line 31 through valved line into the upper part of fractionator 23. When the inhibitor compound or the liquid media comprising it, is of relatively low volatility, a part or all of the stream flowing through line 5| may be passed through valved line 52 containing branched line 53 into fractionator 23 at one or more intermediate points thereof.

Separation of any inhibitor from the resulting alkylate may be effected by any suitable means actions comprise the alkylation, in the presence of hylrogen fluoride-containing catalysts, of a parafiln with a paraflin; an aromatic hydrocarbon with an olefin; aromatic hydrocarbons with alcohols; cycloparaflins with cyclic parafllns and/or cyclic olefins; ethers with aromatics; and other types of alkylation reactions or treatments conducted under alkylati g conditions of any hydrocarbon mixture. The invention furthermore. not to be considered as limited in its application to the execution of reactions of the alkylation type but may be applied broadly to the execution of any organic reactions conducted in the presence'of catalysts comprising hydrogen fluoride. Such reactions comprise among I others, for example, condensations, dehydrations, polymerlzations, molecular rearrangements, isomerization, etc.

This is a division of copending application- Serial Number 518,273, filed January 14, 1944, now Patent No. 2,431,715.

The invention claimed is:

1. In a catalytic hydrocarbon conversion process wherein hydrocarbons are contacted under. conversion conditions with a catalyst comprising hydrogen fluoride in a reaction zone comprising'a metal-containing surface in direct contact with said catalyst, said metal-containing surface being subject to corrosion by said catalyst, the method of inhibiting corrosion of said metal surface which comprises injecting into said reaction zone at a plurality of intermediate points along the length thereof a halide of a metal of groups IV and V of the periodictable.

2. In a catalytic hydrocarbon conversion proc-' ess wherein an admixture of hydrocarbons and a catalyst comprising hydrogen fluorideis passed through a system of apparatus comprising a reaction zone wherein said admixture is subjected to conversion conditions, said apparatus providing metal-containing surfaces in direct contact with said catalyst, said metal-containing comprising, for example, one or more of such steps as water-washing. washing with alkal'ne solutions, distillation, fractionation, scrubbing, solvent extraction. treatment with solid adsorptive materials at normal or elevated temperatures, etc. When utilizing only relatively low concentratlons of the inhibitor, it will often be unnecessary to effect the removal -of the small amounts of entrained material from the alkylate product.

surface being subject to corrosion by said catalyst,

the method of inhibiting corrosion of said metal surfaces which comprises injecting into said system at a plurality of points thereof a fluoride of a metal of groups IV and V of the periodic table.

3. In a catalytic hydrocarbon conversion process wherein an admixture of hydrocarbons and a catalyst comprising hydrogen fluoride is passed through a system of apparatus comprising a reaction zon'e wherein said admixture is subjected to conversion conditions, said appar'atusproviding metal-containing surfaces in direct contact with said catalyst, said metal-containing surface being subject to corrosion by said catalyst, the method of inhibiting corrosion of said metal surfaces which comprises injecting into said system at a plurality of points thereof a fluoride of antimony. 1

4. In a catalytic hydrocarbon conversion process wherein an admixture of hydrocarbons and a catalyst comprising hydrogen fluoride is passed through asystem of apparatus comprising a reaction zone wherein said admixture vis subjected to conversion conditions, said apparatus providing metal-containing surfaces in direct contact with said catalysts, said metal-containing surface being subject to corrosion by said catalyst, the method of inhibiting corrosion of said metal surfaces which comprises injecting into said system at a plurality of points thereof a fluoride of arsenic.

5. In a catalytic hydrocarbon conversion procand introducing said portion of the hydrocarbon charge containing said metal halide into the reaction zone at a plurality of spaced points along the length thereof.

6. In a catalytic hydrocarbon conversion process wherein hydrocarbons and a catalyst comprising hydrogen fluoride are introduced into a conversion zone providing a metal-containing surface indirect contact with said catalyst and the resulting mixture isdsubjected to hydrocarbon 10 riodic table and passing eflluence comprising hydrocarbons at least partlysaturated with respect to said metal halide from said vessel into said conversion zone at a plurality of spaced points alcng the length thereof. 9. ,In a catalytic-hydrocarbon conversion process wherein hydrocarbons are contacted under conversion conditions with a catalyst comprising Q hydrogen fluoride in a conversion zone comprising a metal-containing surface in direct contact with said catalyst, said metal-containing surface being subject to corrosion b said catalyst,'the

improvement which comprises diverting a portion of the hydrocarbon and catalyst charge to said conversion zone through a vessel containing a halide of a metal of groups IV and V of the peconversion conditions in said conversion zone,

said metal-containing surface being subject to corrosion by said catalyst, the improvement which comprises adding a halide of a metal of roups IV and V to a portion of said catalyst and separately introducing said portion of catalyst containing said metal halide into said conversion zone at a plurality of spaced points along the length thereof.

7. In a catalytic hydrocarbon conversion proc-' ess wherein hydrocarbons are contacted under conversion conditions with a catalyst comprising hydrogen fluoride in a conversion zone comprising a metal-containing surface indirect contact with said catalyst, said metal-containing surface being subject to corrosion by said catalyst, the improvement which comprisesdiverting a portion of the hydrocarbon and catalyst charge to said conversion zone through a vessel containing a halide of a, metal of groups IV and V of the periodic table and passing efliuence comprising hydrocarbons at least partly saturated'with respect to said metal halide from said vessel into said conversion zone.

8.- In a catalytic hydrocarbon conversion process wherein hydrocarbons are contacted under. conversion conditions with a-catalyst comprising hydrogen fluoride in a conversion zone comprising a metal-containing surface in direct contact with said catalyst. said metal-containing surface being subject to corrosion by said catalyst. the improvement which comprises diverting a portion. of the hydrocarbon-and catalyst charge to said conversion zone through a vessel containing a halide of a, metal of groups IV and V0! the pericdic table, the ratio of catalyst to hydrocarbon entering said vessel being less than the ratio of catalyst to hydrocarbon in said conversion zone, and passing eflluence comprising hydrocarbons at least partly saturated with respect to said metal halide from said vessel into said conversion zone.

10. In an alkylation process wherein an alkylatable paraffinic hydrocarbon is contacted with an olefin in the presence of a catalyst comprising hydrogen fluoride at alkylating conditions in a conversion zone providing a metal-containing surface in direct contact with said catalyst, said metal-containing surface being. subject to corrosion by said catalyst, the improvement which comprises diverting a portion of said alkylatabie plurality of spaced points along the length 40 thereof.

AARON WACHTER.

- narnanncas crrnn The l'ollowing references are of record in the ills of this patent:

' UNITED STATES PATENT/5 Number Name Date 2,068,868 Pier et al Jan. 28, 1937 2,325,052 Grosse et a1. July 27, 1943 2,378,762 Frey June 19, 1945 2,378,763 Frey June 19, 1945 2,394,908 Frey -Feb. 12, 1946 2,406,954. Linn Sept. 3, 1948 

